PhD Dissertation submitted to the Faculty of the Virginia Tech
in partial fulfillment of the requirements for
the degree of

DOCTOR OF PHILOSOPHY

in

MATERIALS ENGINEERING SCIENCE

Approved

G. L. WILKES, Chair
T. C. WARD
H. MARAND
R. G. KANDER
D.A. DILLARD

February 14, 1997
Blacksburg, Virginia

Abstract

High density polyethylene (HDPE) films having simple and well-defined stacked lamellar morphology, either with or without a distinct presence of row-nucleated fibril structures, have been utilized as model materials to carry out investigations on solid state structure-property relationships. Four different subjects that were addressed are: 1) mechanical properties and deformation morphologies, 2) orientation anisotropy of the dynamic mechanical a relaxation, 3) orientation dependence of creep behavior, and 4) crystalline lamellar thickness and its distribution.
For the first three topics, appropriate mechanical tests, including tensile (INSTRON), creep (TMA), and dynamic mechanical (DMTA) tests, were performed at different angles with respect to the original machine direction (MD) of the melt extruded films; morphological changes as a result of these mechanical tests were detected by WAXS, SAXS, and TEM. For the forth topic, crystalline lamellar thickness and its distribution were determined by DSC, SAXS, TEM and AFM experiments.
In the large strain deformation study (chapter 4.0), samples were stretched at 00°, 45° and 90° angles with respect to the original MD. A distinct orientation dependence of the tensile behavior was observed and correlated to the corresponding deformation modes and morphological changes, namely 1) lamellar separation and fragmentation by chain slip for the 00° stretch, 2) lamellar break-up via chain pull-out for the 90° stretch, and 3) lamellar shear, rotation and break-up through chain slip and/or tilt for the 45° stretch. A strong strengthening effect was observed for samples with row-nucleated fibril structures at the 00° stretch; whereas for the 90° stretch, the presence of such structures significantly limited deformability of the samples.
In the dynamic strain mechanical a relaxation study (chapter 5.0), samples were tested at nine different angles with respect to the original MD, and the morphologies of samples before and after the dynamic tests were also investigated. The mechanical dispersions for the 00° and 90° tests were believed to arise essentially from the crystalline phase, and they contain contributions from two earlier recognized sub-relaxations of aI and aII. While for the 45° test, in addition to a high temperature aII relaxation, a interlamellar shear induced low temperature mechanical relaxation was also observed. It is concluded that the low temperature relaxation is related to the characteristics of the interface between the crystalline lamellae and amorphous layers.
In the small strain creep study (chapter 6.0), samples were tested at the 00°, 45° and 90° angles at the original MD. Both creep strain and creep rate for samples at the three angles were very different. An Eyring-rate model was utilized to analysis the observed creep behavior, and structural parameters associated with this model, including population of creep sites, activation energy and volume, were obtained by fitting the experimental data to the Eyring-rate equation. It was concluded that the plateau creep rate in these model materials is primarily controlled by the density and physical state of tie-chains in the amorphous phase.
For the lamellar thickness and distribution study, DSC, SAXS, TEM and AFM experiments were conducted for samples having a well-defined stacked lamellar morphology. It was found that the most probable lamellar thickness from SAXS and TEM agreed very well; however, these values did not match with those obtained by DSC and AFM. It was pointed out that the use of DSC to determine lamellar thickness and distribution is so sensitive to heating rate and numerical values for the parameters in the Gibbs-Thomson equation that it is not believed to be suitable for quantitative analysis.

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